[0001] This invention relates to an oxygen sensor element, and more particularly to an oxygen
sensor element which detects oxygen concentration by means of a concentration cell
having electrodes carried by solid electrolyte material.
[0002] Hitherto to detect oxygen concentration in for instance automobile exhaust gas, various
oxygen sensors have been used; namely an oxygen sensor having electrodes disposed
on opposite surfaces of a cylindrical solid electrolyte, an oxygen sensor having a
built-in heater for ensuring regular operation even when exposed to low- temperature
exhaust gas whose temperature is as low as below 300°C, or a lean burn type oxygen
sensor suitable for gas with an air-fuel ratio indicating excess air. As to the shape
of the solid electrolyte in oxygen sensors, a cylindrical solid electrolyte with a
bottom board and a laminated structure formed of plate-like or film-like solid electrolytes
overlaid one above the other have been proposed and used.
[0003] The conventional arrangement of disposing a pair of electrodes on opposite surfaces
of a film-like solid electrolyte (see for example US-A-4282080) has shortcomings in
that the difference in both the thermal expansion and the firing shrinkage between
the solid electrolyte and the electrodes tend to cause stress in the solid electrolyte,
and when a sudden temperature change occurs or after continuous operation over a long
period of time, various adverse effects are caused, such as the occurrence of cracks
in the solid electrolyte, an increased error in the output electromotive force, of
breakage of the oxygen sensor element. Such shortcomings are particularly noticeable
in the case of thin film-like solid electrolytes.
[0004] Referring to Fig. 1 showing the structure of a laminated type oxygen sensor element
of the prior art, film-like or plate-like solid electrolytes are overlaid one above
the other, and a reference electrode 4 is spaced from a heater 11 by a gap portion
7 for introducing a reference gas such as air into the sensor element. Accordingly,
the efficiency of heat transmission from the heater 11 to the reference electrode
4 is low, and the reduction of impedance between a solid electrolyte 2 and the reference
electrode 4 has been delayed, especially immediately after the start of the sensor
operation. Thus, the structure of Fig. 1 has a shortcoming of being slow during start-up.
[0005] Therefore, a first object of the present invention is to provide an oxygen sensor
element in which a solid electrolyte is at least partly protected from the occurrence
of cracks by reducing or suppressing the stress between the solid electrolyte and
one or more electrodes tightly secured thereto.
[0006] A second object of the present invention is to provide an oxygen sensor element which
is at least partly protected from warping and cracking due to the difference in firing
shrinkage between a solid electrolyte and electrodes.
[0007] The invention is set out in claim 1.
[0008] By the invention it is possible to provide an oxygen sensor element which has a built-in
heater disposed in such a manner that heat from the heater is efficiently transmitted
to a reference electrode, so as to ensure quick start of the sensor element by rapidly
reducing its internal impedance at the start of its operation.
[0009] To this end, it is preferred that a heater element, preferably a ceramic heater layer,
is provided in the oxygen sensor element of the invention, which heater in the stacked
layers directly underlies the reference electrode and is separated therefrom only
by one or more of the layers of the sensor element. For instance, the ceramic heater
layer is mounted in tight contact with that surface portion of the second planar electrolyte
which portion does not carry the reference electrode.
[0010] There are two reasons why the invention uses the reference electrode mounted on the
second planar solid electrolyte and the measuring electrode mounted on the first planar
solid electrolyte.
[0011] The first reason is as follows; namely, if a reference electrode and a measuring
electrode made of platinum or the like are to be mounted on opposite surfaces of one
planar solid electrolyte, the reference electrode is generally a cermet electrode
which can be fired simultaneously with the green sheet of the planar solid electrolyte,
while the measuring electrode is generally made of a similar cermet electrode, too,
so that an oxygen sensor element with an excellent durability can be produced by sintering
all of them simultaneously. Preferably, the planar solid electrolyte between the measuring
electrode and the reference electrode should be thin, to reduce the impedance of the
oxygen sensor element and to ensure proper operation at low temperatures.
[0012] However, when platinum electrodes or other cermet electrodes are disposed on opposite
surfaces of one planar solid electrolyte, the difference in the coefficient of thermal
expansion between the solid electrolyte and such electrodes results in a stress therebetween,
and upon occurrence of sudden temperature change or after a continuous operation over
a long period of time, the stress tends to cause cracks in the solid electrolyte.
To reduce such stress, in the oxygen sensor element of the invention, the first planar
solid electrolyte has only one side surface thereof carrying one electrode, while
the other electrode is disposed on the second planar solid electrolyte. In this way,
the stress on the first planar solid electrolyte is reduced to one-half, so as to
prevent the first planar solid electrolyte from cracking.
[0013] The second reason is as follows: namely, when it is desired to produce a plate-like
oxygen sensor having a reference electrode facing a central hollow portion and a measuring
electrode disposed on one side surface thereof, the best result with a high durability
is achieved, as a rule, by assembling component sheets through superposition of green
sheets or printing, and then firing or sintering them at once.
[0014] However, the firing shrinkage of the solid electrolyte generally differs from that
of the cermet electrodes. Especially, if cermet layers for electrodes are applied
to opposite surfaces of the first electrolyte green sheet, a very large difference
of firing shrinkage is caused between the first solid electrolyte and the second solid
electrolyte having no electrodes, resulting in possible warping and separation of
solid electrolyte layers and cracks therein. To suppress such difference in firing
shrinkage, the present invention uses different electrodes mounted on different solid
electrolytes respectively, so as to obviate the above- mentioned shortcomings caused
by such difference in firing shrinkage.
[0015] The reason for the prefered arrangement with a heater arranged as described above
is as follows: namely, the reference gas to be in contact with the reference electrode
is air in most cases, and platinum is widely used in the reference electrodes.
[0016] However, the activity of platinum is gradually reduced when it is heated in air over
a long period of time, and an increasingly high temperature becomes necessary for
ensuring the proper impedance level at the platinum electrode. On the other hand,
the reduction of the activity of the measuring electrode due to expose to engine exhaust
gas is relatively small. Accordingly, the conventional oxygen sensor with a heater
to heat its sensor element has a shortcoming in that the time necessary for starting
the sensor by heating the reference electrode gradually increases as the sensor is
used.
[0017] To shorten the time necessary for the heating up and to efficiently transmit heat
from the heater to the reference electrode, the heater directly underlies the reference
electrode and is separated only by one or more of the layers of the sensor element.
[0018] In this way, the reference electrode is heated quickly to a high temperature.
[0019] In another embodiment of the invention, porous ceramics or porous solid electrolyte
is disposed in the reference gas space. By this, the internal impedance of the oxygen
sensor is reduced and the mechanical strength of the oxygen sensor element is improved
by the presence of such porous ceramics or porous solid electrolyte in the otherwise
hollow gap portion, while allowing effective contact of the reference electrode with
the reference gas and without causing any adverse effects on the above-mentioned features
of the invention.
[0020] An oxygen sensor element of the present invention may include a pair of electrodes
forming an oxygen pump, and a DC voltage may be applied across such pair of oxygen
pump electrodes to apply a direct current thereto. In this way, an amount of oxygen
proportionate to the amount of electric charge of the direct current may be moved
from one electrode to the other electrode of the oxygen pump. At least one of the
electrodes forming the oxygen concentration cell may be used in common with that of
the oxygen pump.
[0021] Embodiments of the invention, will now be described by way of example with reference
to the accompanying drawings, in which:
Fig. 1 is a schematic exploded view of the typical oxygen sensor element of the prior
art described above;
Fig. 2 and Fig. 3 are schematic exploded views of two embodiments of the oxygen sensor
element according to the present invention;
Fig. 4 is an explanatory diagram of a practical example of the invention which is
described below; and
Fig. 5 and Fig. 6 are schematic exploded views of other embodiments of the oxygen
sensor element according to the present invention.
[0022] In the different views of the drawings, 1 is an oxygen sensor element, 2 is a first
solid electrolyte, 3 is a measuring electrode, 4 is a reference electrode, 3', 4'
are lead wires with terminals, 5 is a porous ceramic layer, 6, 6' are gastight layers,
7 is a gap portion, 7' is a porous ceramics or solid electrolyte, 8 is a gastight
solid electrolyte, 9 is a second solid electrolyte, 10 is a gastight layer, 11 is
a heater, 11' is a lead wire with a terminal, 12 is a flange-engaging portion, 13
is an insulating layer, 19 is an electrode, 19' is a lead wire with a terminal, 20
is a diffusion hole, 21 is a cavity, 22 is a solid electrolyte, 23 is an electrode,
and 23' is a lead wire with a terminal.
[0023] Fig. 2 shows a schematic exploded view of an oxygen sensor element of laminated type
made by using plate-like solid electrolytes, as an embodiment of the invention. In
the illustrated oxygen sensor element 1, a first solid electrolyte 2 made of zirconia
ceramics ot the like carries a porous measuring electrode 3 mounted on one side surface
thereof, and the measuring electrode 3 is for instance made of platinum. A similarly
porous reference electrode 4 is mounted on one side surface of a second solid electrolyte
9. The first solid electrolyte 2 and the second solid electrolyte 9 are connected
to each other with an intermediate solid electrolyte 8 disposed therebetween, so as
to form an oxygen concentration cell.
[0024] The electrodes 3 and 4 have lead wires with terminals 3' and 4' connected thereto
respectively, and the terminals 3' and 4' are disposed so as to be exposed to the
outside of the oxygen sensor element 1. The measuring electrode 3 comes in contact
with a gas being measured through a porous ceramic layer 5 made of for instance spinel.
The porus ceramic layer 5 is enclosed by a gastight layer 6 made of zirconia or the
like. The reference electrode 4 is exposed to a gap portion 7 defined in the gastight
solid electrolyte 8. The gap portion 7 is surrounded by the first solid electrolyte
2, the second solid electrolyte 9, and the gastight solid electrolyte 8. A reference
gas such as air is introduced in the gap portion 7.
[0025] Instead of leaving the gap portion 7 hollow, a porous ceramics or solid electrolyte
7' may be fitted in the gap portion 7, as shown in Fig. 3. When the reference gas
is fed into interstices of the porous ceramics or solid electrolyte 7', the
[0026] reference electrode 4 comes in contact with the reference gas, and at same time,
the impedance across the reference electrode 4 and the measuring electrode 3 is reduced
by the presence of the porous ceramics of solid electrolyte 7', as compared with the
case of leaving the gap portion 7 hollow. The porous ceramics or solid electrolyte
7' also acts to improve the mechanical strength of the oxygen sensor element 1 around
the electrodes 3 and 4 therof. The requirement for the porous ceramics of solid electrolyte
7' is to be pervious to the reference gas, and a preferable material for it is porous
zirconia.
[0027] The embodiment of Fig. 3 has a gastight layer 10 carrying a heater 11 mounted on
one side surface thereof. Opposite ends 11' of two lead wires for the heater 11 are
disposed so as to be exposed to the outside at the surface of the oxygen sensor element
1. When assembled, the oxygen sensor element 1 can be mounted on a suitable flange
(not shown) at a flange-engaging portion 12. The heat from the heater 11 is transmitted
to the reference electrode 4 through an electrically insulating layer 13 and the second
solid electrolyte 9. The heater 11 can be heated by an alternating current (AC) or
a direct current (DC). When DC is used, the gastight layer 10 and the insulting layer
13 are preferably made of alumina ceramics or other suitable insulating material.
If only AC is used, the gastight layer can be made of solid electrolyte such as zirconia
ceramics, and the insulating layer 13 may be dispensed with.
[0028] The embodiment of Fig. 3 is particularly useful in the case of using a DC power source,
and in this case the insulating layer 13 provides a high insulation between the heater
11 and the reference electrode 4. To ensure good heat transmission, the thickness
of the insulating layer 13 is preferably less than 50 pm.
[0029] From the standpoint of durability, the heater 11 is preferably made of a metal such
as nickel, silver, gold, platinum, rhodium, palladium, indium, ruthenium, tungsten,
molybdenum, an alloy thereof, and the like. However, an electrically conductive ceramic
compound such as zinc suboxide, lanthanam chromite (LaCr0
3), lanthanum boride (LaB
6), silicon carbide (SiC), and the like, can be also used to form a ceramic heater
as the heater 11.
[0030] Fig. 4 shows one example of the present invention now specifically described. A 1.5
mm thick zirconia green sheet consisting of 96 mol % of zirconia (Zr0
2) and 4 mol % of yttria (Y
20
3) was prepared for making the second solid electrolyte 9. Conductive layers for the
reference electrode 4 and the lead wire and terminal 4' were printed on one side surface
of the zirconia green sheet using a cermet material consisting of 80% by weight of
platinum and 20% by weight of zirconia (Zr0
2). A 50 pm thick paste layer of zirconia ceramics material for making the porous solid
electrolyte 7' was printed thereon. A 50 pm thick zirconia material layer for the
first solid electrolyte layer 2 was printed thereon by using a paste consisting of
96 mol % of zirconia (Zr0
2) and 4 mol % of yttria (Y
20
3). Conductive layers for the measuring electrode 3 and the lead wire and terminal
3' were printed on the zirconia material layer using the same cermet material as for
the reference electrode 4.
[0031] The green body prepared by the above printings was fired at 1,400°C for 2 hours,
and an oxygen sensor element 1 according to the present invention was produced.
[0032] No cracks were found in the first solid electrolyte 2 of the thus produced oxygen
sensor element 1. It was confirmed by tests that the oxygen sensor element 1 thus
produced operated satisfactorily in engine exhaust gas at 400°C. The formation of
the oxygen sensor element of the invention is not restricted to the foregoing embodiments
and example. Fig. 5 and Fig. 6 show structures of other embodiments or laminated structures
made by overlaying a number of layers one above the other. More specifically, the
embodiment of Fig 5 is the so-called lean burn type oxygen sensor element. In this
embodiment, a first solid electrolyte 2 and a second solid electrolyte 9 are bonded
to opposite surfaces of an intermediate gastight solid electrolyte 8, and a pair of
electrodes 3, 4 forming an oxygen concentration cell and another pair of electrodes
19, 4 forming an oxygen pump are mounted on the solid electrolytes 2 and 9. The reference
electrode 4 is used in common for both the oxygen concentration cell and the oxygen
pump.
[0033] Gas to be measured is introduced into a cavity 21 through a diffusion hole 20 so
as to come in contact with the measuring electrode 3. Due to the action of the oxygen
pump, the oxygen partial pressure in the cavity 21 can be reduced to a level below
that in the gas being measured at the outside of the oxygen sensor element 1. Having
such oxygen pump incorporated therein, the oxygen sensor element of Fig. 5 can be
used for the controal of an engine which exhausts the so-called lean burn gas having
a higher oxygen partial pressure than that of the theoretical air-fuel ratio.
[0034] Fig. 6 shows a modification of the oxygen sensor element of Fig. 5. In this modification,
an oxygen concentration cell is made by using the solid electrolytes 2, 8, and 9 for
holding the electrodes 3 and 4 in the same manner as the preceding embodiments, while
an oxygen pump is made by using a completely separate set of electrodes 19 and 23
carried by a solid electrolyte 22 on opposite surfaces thereof. Lead wires with terminals
19' and 23' are formed on the opposite surface to the electrodes 19 and 23 as shown
in Fig. 6. The function of the oxygen pump formed of the electrodes 19 and 23 across
the solid electrolyte 22 is similar to what has been described above for Fig. 5.
[0035] In the embodiments of Fig. 5 and Fig. 6, flange-engaging portions 12 fulfil the same
function as the flange-engaging portion 12 of Fig. 3.
[0036] As described in the foregoing, an oxygen sensor element according to the present
invention uses a measuring electrode and a reference electrode mounted on separate
solid electrolyte layers, so that even if thin solid electrolyte layers are used to
hold any of the electrodes, there is small or no risk of cracking of the solid electrolytes.
Thus, the oxygen sensor element of the invention can have a high reliability and be
suitable for mass production.
[0037] Further, the oxygen sensor element of the invention can have a heater facing the
reference electrode only through a solid electrolyte layer without any gap, so that
the heat from the heater is efficiently transmitted to the reference electrode. Accordingly,
the impedance of the oxygen sensor element is quickly reduced by the heater, especially
at the start of the sensor operation, so as to put the oxygen sensor into operation
in a very short time while enabling a saving in power consumed at the heater.
[0038] Therefore, the oxygen sensor element of the invention is particularly suitable for
detection and control of the oxygen concentration in automobile exhaust gas, so that
the oxygen sensor element of the invention is very useful in various industries producing
exhaust gas.
[0039] In this specification, the layers are described as planar, which means generally
planar but does not exclude some deviation from strict planarity, e.g.for manufacturing
reasons as shown in Fig. 4.
1. Sauerstoffsensor mit mehreren gestapelten ebenen Schichten (2, 6, 8, 9, 10, 13),
mit oder bestehend aus Festörper-Elektrolytschichten, einem in den gestapelten Schichten
angeordneten Hohlraum (7) für eine Bezugssubstanz, der durch mindestens zwei der Schichten
begrenzt ist, und eine Meßelektrode (3) und eine Bezugselektrode (4) die mit den Festkörper-Elektrolytschichten
in Berührung steht, um eine Konzentrationszelle zu bilden, wobei die Bezugselektrode
dem Hohlraum für die Bezugssubstanz zugekehrt ist, dadurch gekennzeichnet, daß die
Meßelektrode (3) auf einer Seite einer ersten Festkörper-Elektrolytschicht (2) angeordnet
ist, deren gegenüberliegende Seite dem Hohlraum (7) für die Bezugssubstanz benachbart
ist, und daß die Bezugselektrode (3) auf einer Seite einer zweiten Festkörper-Elektrolytschicht
(9) angeordnet ist, so daß sie über den Hohlraum für die Bezugssubstanz hinweg der
gegenüberliegenden Seite der ersten Festkörper-Elektrolytschicht (2) zugekehrt ist.
2. Sauerstoffsensor nach Anspruch 1 mit einem Heizelement (11), das in den gestapelten
Schichten unmittelbar unter der Bezugselektrode (4) angeordnet und von dieser nur
durch eine oder mehrere der Schichten getrennt ist.
3. Sauerstoffsensor nach Anspruch 2, wobei das Heizelement (11) ein keramisches Heizelement
ist.
4. Sauerstoffsensor nach einem der Ansprüche 1 bis 3, wobei der Hohlraum für die Bezugssubstanz
ein mit einem Bezugsgas zu füllender Spalt ist.
5. Sauerstoffsensor nach einem der Ansprüche 1 bis 3, wobei der Hohlraum für die Bezugssubstanz
ein poröses Keramikmaterial enthält.
6. Sauerstoffsensor nach einem der Ansprüche 1 bis 3, wobei der Hohlraum für die Bezugssubstanz
einen porösen Festkörper-Elektrolyt enthält.
1. Capteur d'oxygène comprenant un certain nombre de couches planes empilées (2, 6,
8, 9, 10, 13) comprenant ou consistant en couches d'électrolyte solide, un espace
de substance de référence (7) dans les couches empilées défini par au moins deux des
couches et une électrode de mesure (3) et une électrode de réference (4) en contact
avec les couches d'électrolyte solide afin de former une cellule de concentration
avec l'électrode de référence exposée audit espace de substance de référence caractérisé
en ce que ladite électrode de mesure (3) est montée sur une surface d'une première
couche d'électrolyte solide (2) dont la surface opposée est adjacente audit espace
de substance de référence (7) et ladite électrode de référence (4) est montée sur
une surface d'une seconde couche d'électrolyte solide (9) afin de se trouver face
à la surface opposée de la première couche d'électrolyte solide (2) à travers l'espace
de substance de réference.
2. Capteur d'oxygène selon la revendication 1 ayant un élément réchauffeur (11) qui,
dans les couches empilées, se trouve directement en-dessous de l'électrode de référence
(4) et en est séparé uniquement par une ou plusieurs desdites couches.
3. Capteur d'oxygène selon la revendication 2, où l'élément réchauffeur (11) est un
élément réchauffeur en céramique.
4. Capteur d'oxygène selon l'une quelconque des revendications 1 à 3, où l'espace
de substance de référence est un espace à remplir du gaz de référence.
5. Capteur d'oxygène selon l'une quelconque des revendications 1 à 3, où ledit espace
de substance de référence contient une matière céramique poreuse.
6. Capteur d'oxygène selon l'une quelconque des revendications 1 à 3, où ledit espace
de substance de référence contient un électrolyte solide poreux.